Electrostatic and nonelectrostatic, conventional and unitary thermodynamic quantities of reaction. II. Proton–ligand and metal–ligand reactions in mixed solvents

Abstract

A calculation method of the electrostatic and the nonelectrostatic parts of thermodynamic quantities of reaction, previously proposed and applied to association reactions in aqueous medium, is applied, in the present work, to reactions in mixed solvents. The aim of the present treatment is to clarify the importance of the various factors (dependent and independent of the dielectric constant) through which the solvent affects complex stability. The method is applied to ΔG0, ΔH0, and ΔS0 data of literature for proton–ligand and metal–ligand reactions in several water–methanol, water–ethanol, and water–dioxane mixtures. The conclusions of the present study seem to confirm a leading role of solvation equilibria in determining different stabilities of complex in different solvents, while a minor role is assigned to the dielectric properties of the solvent.